Synthesis of Three Stereoisomeric Forms of 2,8-Dimethyl-1,7-dioxaspiro[5.5]undecane, the Main Component of the Cephalic Secretion of Andrena wilkella

Mori, Kenji; Tanida, Kaichi

doi:10.3987/s-1981-02-1171

Cited by 24 publications

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“…Reduction of ethyl acetoacetate (A) with fermenting baker's yeast gives (S )-B. Synthesis of (2S,6R,8S )-88 was executed as a part of this project (Figure 4.35). 64,65 The hydroxy ester (S )-B (92% ee) was converted to iodide (S )-C (4 steps). Inversion of the configuration of (S )-B to (R)-D was possible by means of Mitsunobu inversion, which was further converted to (R)-C. Accordingly, both the enantiomers of C were prepared from the single enantiomer (S )-B. Alkylation of the dianion of methyl acetoacetate with (S )-C gave E, whose further alkylation with (S )-C afforded F. Successive treatments of F with base followed by acid effected hydrolysis, decarboxylation and acetalization to give ( 3 ± 0.7 (pentane) and +44.6 ± 0.7 (pentane), respectively.…”

Section: Preparation Of a Pure Sample For Bioassay (3) Pheromone Of mentioning

confidence: 99%

Synthesis of Pheromones

Mori

2010

Chemical Synthesis of Hormones, Pheromones and Other Bioregulators

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Section: Preparation Of a Pure Sample For Bioassay (3) Pheromone Of mentioning

confidence: 99%

Synthesis of Pheromones

Mori

2010

Chemical Synthesis of Hormones, Pheromones and Other Bioregulators

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“…This class of compounds has been identified from bark beetles as well as from wasps and bees.s5 Francke et al identified trans, transand cis, trans-2,8-dimethyl-l,7dioxaspiro[5.5]undecane, (1) and (2), respectively, in the mandibular gland secretion of Adrena bees.3.4 Mori and Tanida have reported a synthesis of the enantiomers of (1) by a multistep procedure.6 This, however, failed to produce the enantiomers of ( 2 ) . 6 The racemic spiroacetals (1) and (2) are conveniently prepared as a 3 : 2 mixture according to the method described by Francke et al 7 The diastereoisomers could easily be separated by preparative g.1.c. (column OV 351, 6 ft).…”

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Preparative separation of the enantiomers of trans,trans- and cis,trans-2,8-dimethyl-1,7-dioxaspiro[5.5]undecane, main pheromone components of Adrena bees, by liquid chromatography on triacetycellulose

Isaksson¹,

Liljefors²,

Reinholdsson³

1984

J. Chem. Soc., Chem. Commun.

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TheMitsunobu Reaction

1992

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Alkyl and aryl phosphites and phosphines react with compounds having weak heteroatom–heteroatom bonds, such as SS, OO, etc., and with azo compounds to form reactive phosphonium salts. These phosphonium salts in turn promote “redox” condensation reactions with compounds having active hydrogens. The condensation reaction of alcohols using the redox couple of a triaryl‐ or trialkylphosphine and a dialkyl azodicarboxylate has become known as the Mitsunobu reaction, based on his pioneering work in the late 1960s. The overall reaction is summarized, wherein the alcohol (R 1 OH) and acidic compound (H–Nu) are condensed to form product (R 1 –Nu), while triphenylphosphine is oxidized to triphenylphosphine oxide and the azodicarboxylate is reduced to the hydrazine. Although the typical redox combination is diethyl azodicarboxylate (DEAD) and triphenylphosphine, many other combinations have found selected use. The reaction is generally limited to primary and secondary alcohols, although tertiary alcohols react in a few intramolecular and intermolecular reactions. For secondary alcohols the reaction usually proceeds with clean inversion of stereochemistry. The acidic component of the reaction generally has an aqueous p K a < 15, with intramolecular reactions providing the exceptions. Examples of H–Nu include oxygen nucleophiles such as carboxylic acids and phenols; nitrogen nucleophiles such as imides, hydroxamates, and heterocycles; sulfur nucleophiles such as thiols and thioamides; and carbon nucleophiles such as β‐ketoesters. Major reviews of the Mitsunobu reaction were published in 1981 by Mitsunobu and in 1983 by Castro. The former review concentrated on reactions using DEAD/triphenylphosphine, while the latter review focused on reactions in which halogens replaced the hydroxy group using reagents such as triphenylphosphine/carbon tetrachloride, triphenyl phosphite/iodomethane, and triphenylphosphine/ N ‐halosuccinimide. Reactions involving the DEAD/triphenylphosphine redox system are the principal subject of this chapter, with emphasis on the literature between 1981 and 1988.

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Synthesis of Three Stereoisomeric Forms of 2,8-Dimethyl-1,7-dioxaspiro[5.5]undecane, the Main Component of the Cephalic Secretion of Andrena wilkella

Cited by 24 publications

References 0 publications

Synthesis of Pheromones

Synthesis of Pheromones

Preparative separation of the enantiomers of trans,trans- and cis,trans-2,8-dimethyl-1,7-dioxaspiro[5.5]undecane, main pheromone components of Adrena bees, by liquid chromatography on triacetycellulose

TheMitsunobu Reaction

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